Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43-55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20-43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

Effect of sulfide on the cytotoxicity of arsenite and arsenate in human hepatocytes (HepG2) and human urothelial cells (UROtsa)

Arsenic, a common poison, is known to react with sulfide in vivo, forming thioarsenates. The acute toxicity of the inorganic thioarsenates is currently unknown. Our experiments showed that a fourfold sulfide excess reduced acute arsenite cytotoxicity in human hepatocytes (HepG2) and urothelial cells (UROtsa) significantly, but had little effect on arsenate toxicity. Speciation analysis showed immediate formation of thioarsenates (up to 73 % of total arsenic) in case of arsenite, but no speciation changes for arsenate. Testing acute toxicity of mono- and trithioarsenate individually, both thioarsenates were found to be more toxic than their structural analogue arsenate, but less toxic than arsenite. Toxicity increased with the number of thio groups. The amount of cellular arsenic uptake after 24 h corresponded to the order of toxicity of the four compounds tested. The dominant to almost exclusive intracellular arsenic species was arsenite. The results imply that thiolation is a detoxification process for arsenite in sulfidic milieus. The mechanism could either be that thioarsenates regulate the amount of free arsenite available for cellular uptake without entering the cells themselves, or, based on their chemical similarity to arsenate, they could be taken up by similar transporters and reduced rapidly intracellularly to arsenite.     

Sorption of arsenate and arsenite anions by iron(III)-poly(hydroxamic acid) complex

Iron(III)-poly(hydroxamic acid) resin complex has been studied for its sorption abilities with respect to arsenate and arsenite anions from an aqueous solution. The complex was found effective in removing the arsenate anion in the pH range of 2.0 to 5.5. The maximum sorption capacity was found to be 1.15 mmol/g. The sorption selectivity showed that arsenate sorption was not affected by chloride, nitrate and sulphate. The resin was tested and found effective for removal of arsenic ions from industrial wastewater samples.     

除氟活性铝氧化物（AlOxHy-Fn）的吸附除砷性能

以活性铝氧化物AlOxHy处理某高氟地下水的中试实验获得的吸附剂废料AlOxHy-Fn为对象,考察其对三价砷（As（Ⅲ））和五价砷（As（Ⅴ））吸附去除性能,并对吸附机理进行了探讨。研究显示,AlOxHy-Fn为多孔无定型且具有不规则表面的絮状结构,比表面积为218．88m2／g,零电荷点pHZPC在pH为8左右;AlOxHy-Fn可快速吸附As（Ⅲ）和As（Ⅴ）,且反应24h后的平衡吸附量分别为0．60和3．41mg／g,朗格缪尔模型可以很好地描述As（Ⅲ）和As（Ⅴ）在AlOxHy-Fn表面的吸附,且As（Ⅲ）和As（Ⅴ）的最大吸附容量分别为13．63和63．27mg／g;AlOxHy-Fn在pH=4～10范围内对As（Ⅴ）去除率在90％以上,As（Ⅲ）在中性和弱碱性pH范围内吸附效果较好,但去除率仍在32％以下。AlOxHy-Fn表面性质、砷形态分布特征等对As（Ⅲ）与As（Ⅴ）的吸附有重要影响,电负性As（Ⅴ）较电中性As（Ⅲ）更容易吸附在AlOxHy-Fn表面。AlOxHy-Fn吸附除砷过程中,在pH为6时氟溶出量最低（0．40mg／g）,过高或过低pH均会导致氟溶出量增大;氟溶出量与As（Ⅴ）吸附量之间有明显正相关关系（R2=0．97）,但与As（Ⅲ）吸附量无相关关系;铝溶出量在pH为4～10范围内均很低。将AlOxHy-Fn回用作为除砷吸附剂去除工业含砷废水的砷具有良好的技术经济可行性,且将As（Ⅲ）氧化为As（Ⅴ）是提高去除效果的重要手段。     

Influence of redox potential (Eh) on the availability of arsenic species in soils and soils amended with biosolid

A study was done on the influence of redox potential on the mobility and availability of the various arsenic chemical forms in a Mollisol soil from central Chile amended with biosolid. Arsenic availability was strongly dependent on the applied redox potential. As expected, under reducing conditions (-200 mV vs Hg/Hg(2)Cl(2)) arsenic availability increased significantly, and arsenic was found mainly as arsenite. On the contrary under oxidizing conditions (200 mV vs Hg/Hg(2)Cl(2)) arsenic solubility decreased markedly and was governed by the presence of arsenate. The greatest concentration of organic arsenic species was found under reducing conditions, which would indicate that methylated species may participate in the transformation of arsenate to arsenite. In biosolid-amended soils the concentrations of methylated species increased as a function of time under reducing conditions, which can be attributed to the greater microbial activity resulting from the organic matter supply from the biosolid to soil. In all the systems, a high concentration of As(V) was found under reducing conditions, indicating that the chemical kinetics for the conversion of arsenate to arsenite is slow. Along time, the content of As(V) increased in the control soils, which may be attributed to the possible dissolution of iron oxides and hydroxides under reducing conditions.     

Influence of sulfide (S2-) on preservation and speciation of inorganic arsenic in drinking water

Generally, H2SO4, HNO3, HCl or the combination of ethylenediaminetetraacetate with acetic acid (EDTA-HAc) have been used to preserve arsenite and arsenate species prior to analysis. When these acidic preservatives are added in sulfidic water, instantaneous precipitation of poorly crystalline orpiment, As2S3(am), occurs, thereby lowering the total arsenic, As(Tot), analysis. A new method for the determination of As(Tot) was developed in which acid-preserved sulfidic water samples were oxidized with NaOCl, converting As2S3(am) and thioarsenic species to arsenate. A new method was also developed for the separation of uncharged arsenite and charged thioarsenic species in fresh, unpreserved sulfidic water by adsorbing the charged thioarsenic species while allowing uncharged arsenite to pass through a strong-base resin unhindered. The adsorbed thioarsenic species could be eluted efficiently with 0.16 M NaOCl solution.     

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

Adsorption/desorption of arsenite and arsenate on chitosan and nanochitosan

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

     

Arsenic species and chemistry in groundwater of southeast Michigan

Groundwater samples, taken from 73 wells in 10 counties of southeast Michigan in 1997 had arsenic concentrations in the range of 0.5 to 278 microg/L the average being 29 microg/l. About 12% of these wells had arsenic concentrations that exceeded the current USEPA's maximum contaminant level of 50 microg/l. Most (53-98%) of the arsenic detected was arsenite [As(III)] and other observations supported the arsenic species distribution (low redox potential and DO). In shallow groundwater (< 15 m), arsenic concentrations are low likely due to the formation of insoluble ferrosoferric hydroxide complex. In deep groundwater (> 15 m), the concentration of arsenic is possibly controlled by reductive dissolution of arsenic-rich iron hydroxide/oxyhydroxide and dissolution of arsenic sulfide minerals.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

Toxicity of arsenate and arsenite on germination, seedling growth and amylolytic activity of wheat

Effects of different concentrations of arsenite and arsenate (0-16 mg/l) on seed germination, relative root length and shoot height, arsenic accumulation in young seedlings, alpha-amylase, beta-amylase and total amylolytic activity in wheat were investigated in order to elucidate the toxicity of arsenic in the early developmental stage. Germination percentages of different wheat varieties had different responses to arsenic species and decreased significantly with increasing arsenic concentrations except Duokang 1. Relative root length (RRL) and relative shoot height (RSH) of wheat seedlings decreased with increasing concentrations of arsenite and arsenate. The relative root lengths were correlated with the relative shoot heights for arsenite (r2 = 0.79) and arsenate (r2 = 0.77). Arsenic uptake by seedlings increased with the increasing concentrations of arsenite or arsenate and followed the Michaelis-Menten kinetics function. The average total amylolytic activity and beta-amylase activity had no significant difference comparable to that of controls at the concentration 2 mg/l arsenite or arsenate, but decreased apparently when the concentration was higher than 2 mg/l. Whereas the alpha-amylase activity decreased with increasing concentrations of arsenite or arsenate over the whole concentration range. Arsenite decreased all the endpoints more remarkably than arsenate. In comparison, shoot height and root length were more sensitive to arsenic than other endpoints and might be used as indicators for arsenic toxicity.     

Arsenic desorption from ferric and manganese binary oxide by competitive anions: significance of pH

Ferric and manganese binary oxide (FMBO) has been used to remediate an arsenic (As)-polluted river in China, but insufficient data was available to (1) evaluate its effects on the environment and (2) propose a feasible strategy of addressing the arsenic-bearing FMBO. The desorption behavior of arsenic in the presence of four competitive anions (i.e., phosphate, silicate, sulfate, and bicarbonate) at different concentrations was investigated with pH ranging from 3 to 11. The presence of these anions promoted the desorption of arsenic from arsenic-bearing FMBO and followed the sequence of phosphate > silicate > sulfate approximately equal to bicarbonate across a wide pH range. Desorption of arsenate (As[V]) was more significant than that of arsenite (As[III]). Sequence dissolution of arsenic-bearing FMBO particles by NH4-oxalate/oxalic acid and hydrochloric acid were performed. The laboratory results indicated that As(III) was primarily occluded in the crystalline parts of the FMBO. The desorption behavior of arsenic could be described by kinetic models using the Elovich and power function equations under different pH conditions and was related to the adsorption of phosphate and silicate. pH played an important role in the desorption of arsenic, because of its effects on the species distribution of anions, surface charge of the arsenic-bearing FMBO, and subsequent electrostatic forces between anions and FMBO.     

Uptake and accumulation behaviour of angiosperms irrigated with solutions of different arsenic species

Uptake and metabolisation of arsenic as a function of both the plant type and the chemical form of arsenic were examined. For this purpose two different plant species (Silene vulgaris and Plantago major) were selected that differed in their vitality and accumulation behaviour on arsenic-loaded substrates. The plants were cultivated on soil and irrigated with aqueous solutions of an inorganic arsenic compound (arsenious acid) and an organic compound (dimethylarsinate). The arsenic species accumulated in the parts of the plants above ground were extracted by PLE and determined using IC-ICP-MS. The concentrations and metabolisation products of arsenic found in the extracts indicate different mechanisms of arsenic uptake and transformation in both angiosperms. The arsenic species pattern showed that S. vulgaris was more arsenic--tolerable than P. major which is attributed to a low arsenate to arsenite concentration ratio in the plant compartments. S. vulgaris was also able to demethylate and reduce dimethylarsinate to form arsenite in a high extent. P. major accumulated only eight times lower concentration of arsenic, and the arsenate to arsenite concentration ratio shifted to higher values. Metabolisation products of dimethylarsinate did not occur under the present experimental conditions. The vitality of the angiosperms seems to be very dependent on the ability of the plant to reduce arsenate to arsenite.     

Preconcentration of trace arsenite and arsenate with titanium dioxide nanoparticles and subsequent determination by silver diethyldithiocarbamate spectrophotometric method.

A novel method of preconcentration of trace arsenite and arsenate by using titanium dioxide nanoparticles as adsorbent was described. The concentrations of preconcentrated arsenite and arsenate were determined by a silver diethyldithiocarbamate spectrophotometric method without desorption. Batch adsorption experiments were carried out as a function of the pH, contact time, amount of titanium dioxide nanoparticles, and solution volume. In the pH range 5 to 6, adsorption rates of arsenite and arsenate were higher than 98%. The calibration coefficient was 0.9991, and the linear range was 0 to 100 microg/L. The developed method was precise, with the relative standard deviation <5% at concentration level of 10 microg/L, with a detection limit (3sigma, n=6) of 0.44 microg/L. The accuracy of the method for total arsenic was validated by standard reference materials (SRM 3103a) (National Institute of Standards and Technology, Gaithersburg, Maryland). The method was also applied to the analysis of arsenite and arsenate in natural water samples to verify the accuracy. The recovery values remained in a narrow range, from 95 to 103%.     

pH对污水污泥中污染物浸出的影响

研究pH对污泥中污染物浸出的影响可以为投海过程中海洋水体酸碱性变化对污泥中污染物浸出的影响及其变化规律提供理论依据。为了得出不同pH值对污泥中污染物浸出的影响,采用CEN/TS 14429：2005浸出实验对上海5个污水处理厂脱水污泥中重金属、溶解性有机碳、溶解性硫化物和主要离子的浸出情况进行了研究,同时分别以超纯水和海水为浸提剂研究在相应pH范围内盐度对上述指标浸出的影响。结果表明,Zn、Cd、Pb和As在酸性和碱性条件下浸出量较高,在中性或接近中性条件下浸出量则最低,且海水中Zn和Cd的浸出量比超纯水中高;Cu在碱性条件下的浸出量明显比酸性条件高;在所研究的pH范围内,5个污泥样品中溶解性有机碳的浸出量均随pH的升高而增高;仅酸挥发性硫含量最高的S5在海水中有较明显的溶解性硫化物浸出;部分污泥样品中的氮在酸性纯水中有较高的浸出量,海水中浸出量较少;而无论海水或纯水中,磷在强酸和强碱条件下均有明显浸出。     

Anion and cation leaching or desorption from activated carbons from municipal sludge and poultry manure as affected by pH.

The conversion of municipal sludge and poultry manure to activated carbon results in a significant ash fraction that contains several different anions and cations. The objectives of this study were to determine whether the select ions are released or leached from virgin carbon into the sorption medium at different pH values. Activated carbon was placed in solutions of pH 1, 5, or 7, and the leaching of six cations (cadmium, chromium, copper, nickel, lead, and zinc) and two anions (arsenate and selenate) was recorded. Considerable quantities of zinc and copper were removed at pH 1 from all carbon sources. However, the amounts leached at pH 5 and 7 were small or undetectable. Our results indicate that leaching or desorption from carbons made from municipal sludge or poultry manure is pH-dependent and occurs readily under highly acidic conditions but minimally under pH conditions typically seen in contaminated water or wastewater.     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.